Casein compound and process of making



Patented Dec. 2 1, 1937 Q uNiTEo .s'r

T es

CASEIN cotrroUNn AND rnoonsslor 1 Henry momma; Bilinbl'llllO, my. f

- No Drawing. ppllcation April as, 1935, semi This inven tion relates tothe productionoi' 1 compounds of casein with metal hydroxides and-s'alts, or with'ammonium salts, particularly those ';'salts which areacidicfor neutral, or those'metal *5 hydroxides so; feebly alkaline thatthey do not act as solvents for 'casein in the presence of water. Thepresent application is in part a continuation of my co-pendingapplication 644,752 filed November-.28, 1932 (now Patent 2,005,730);

taining an amount of water which is preferably substantially less thanthe amount of actual casein, for example containing 15 to 30% of water.

15 This is first roughly mixed with the salt or compound of the metal.The mixture is then thoroughly kneaded together under high pressure, andis extruded in the form of a relatively thin piece or pieces. Finallythe extruded material is' 20 dried and preferably pulverized orotherwise comminuted. If dry casein constitutes the starting material,it can be first mixed with a small,

amount of water or'aqueous liquid, and allowed to stand for a time, toabsorb thes'aid liquid and then mixed with the metal compound. Or if themetal compound is soluble, it maybe dissolved in water, and the caseinsoaked in the solution, the amount of waterbeing as stated above. 'Inaddition to the above mentioned metal compounds or salts, a small amountof alkaline material, preferably a mild a'lkali such as sodiumbicarbonate or borax may also be added to the initial material ifdesired. i v

In carrying out the process, thejmolst mixture 35 is run through asuitable extruding'machine, which contains a conveyer screw rotatingwithin a cylindrical casing, preferably surrounded bya jacket throughwhich'heating or cooling fluids may pass, or a plurality of jackets,some of which 49 may cool the mixture and others may heat the mixture,depending upon what special materials are being employed. Near thedischarge end of the extruding device is a grid or series of grids, 7through which the charge is'fo'rced, in orderto 45 thoroughly knead theingredients together, and maintain the desired amount of pressure uponthe materials in the convolutions of the screw. As-the mixture-passesthrough the screw'press heat may be; generatedbythe reaction and/or18,435. In Great r'z floiaims. "(cacao-e then dried.

ground to a coarse powder. 'This product, which heat maybe supplied bythe jackets referred to or worms, say a sixteenth of an inch indiameter,

Britain December I more or less. The pressur'ecan beregulated by varyingthe size of theholesin the-gridand the extrusion outlets, so as,to givea pressure in the kneading compartment 1 of two, tons per] square inch,more or less. ,The extruded material isv 5 I I,ca ll attention-tothefact that the amount of water in the mixture is comparatively smallwhich isan advantage in the drying operajtions 10 In accordance with thepresent invention, the

- casein may be provided in amoist condition, con- The following tanner;will serve tojillustrate 10 the invention. Example 1v To--100 parts ofair-dried casein, containing. about 10% moisture are added .20 parts ofcold water and the mixture allowed to stand for about an hour, duringwhich time thecasein absorbs the whole of the water, forming a masshaving a mm sistency resemblingwet corn meal. Then 8 parts.

- of ferric hydroxide (containing 15% of water),

are added and the mass mixedby agitation for 10 minutes. The mixture isthen run through the extruding machine, with external heating. Theextrudedjribbon is dried in an oven, and.then

contains about 4.5 Fe is dark brownin color.

It is insoluble in water but readily-soluble m aikalis. It is useful formedicinal purposes. 'iExanrp le 2 I f j v 0 Another casein-ironpreparation maybe made 3 in a similar manner bymixing 5 parts of caseinand 1 part of water, later adding 1 part of iron lactate, kneading andextruding.-- Thislproducti l is insoluble in water but soluble in,alkalis. It may be ground to a fine powder, mixed with 1.5 parts 1 ofwater and 0.72 part of sodium. bicarbonate and again passed throughitheextruding machine, and dried. The flnal dry product, which isIsoluble inwater, contains aboutj 3% Fe. '1 i 40 "Example 3.

treating in the extruding j' achine and finally drying. The end product'containsabout 2% Cu andissolubleinwaterrf v Theparts throughout theexamples are by I weight, and the above examples-are given merely bywayof illustration.

varies with the character ofthedifierent com pounds, a very viscoussolution such as that obtained with the aluminum borate compoundrequiring a greater amount of water to bring it to a thin consistencythan does a thin-flowing solution obtained for instance with theammonium acetate compound, which requires no dilution. In each case 100parts of the dry powder were mixed with '7 parts of ammonia (26 B.) in400 parts of water, heated to 160 F.,

cooled anddiluted 'td'the total water-content shown in column E, exceptthat the compound made with antimony lactate required ".10 parts ofammonia. The viscosity walues recorded in column F were determined atastandardtem perature of 70 F. on a Stoermer viscosimeter (driven by a500- gr. weight) and it is to be understood that the lower the reading,the higher is the viscosity. 7

In column F, are recorded the relative I soluble in water but soluble insuch casein solvents as borax, trisodium phosphate and caustic soda.cium acetate, manganese citrate and strontium salicylate are alsocompletely. soluble in a 10% aqueous solution of sodium acetate whilethe other compounds listed-and casein itself are not soluble. I t d vSome of the compounds may be used with advantagein place of casein formaking glues while others are unsuitable for this purpose. A com- Thecompounds of cobalt carbonate, calparative test in a typical casein glueformula 7 was made as follows: The dryingredients of the dry mixture aremixed with 200 parts of water, initially at a temperature of about. F.and well stirred for, 20 minutes. At this stage the viscosity of theliquid glue is taken on the Stoermerviscosimeter. The: glue is thenallowed to stand andthe viscosity again determined atthe end of 5 'hoursand again at 24 hours. The

vaIues btalned are recorded in columns G,'.H, and. I .ofTable 1.Inturther tests- 75 parts of the selected casein-compound wassubstituted for. 75 parts .of casein in the above formula and themixture stirred in" the same manner with recorded in the. respectivecolumns in Table 1.

Table 1 g In glue annular-vis- Eztruded product Ammoma test I cosity at79F i I C Amounts used 7 asem, I amt. 20min. 5hrs. 25hrs. Metalcompound, name used Casein 26 B water I comp. ammonia A B O D t E F v GT H I V 1 I l 7.63 100 100 7 i 500 8 -,.60 42 5.11 100 100 7 800' -32 107 20 1.15 100 i 7 500 5 34 15= 1. 1 10.5 100 100 7 600 16 j 5. 22 100100 7 600 4 40 "29 l 5. 46 100 100 7 500- r 3 j 6:6, .100 100 7 000 5001 {e11 "3.0 100 100 7 400 3 20 8.35 100 100 7 600 i "28 8.63 100 100 7500 7 -13 16 10.8 100 100 7 500 7 I 17 10.1 100 100 10 400 l 27 31 3. 52100 100 7 600 3 28 6:82 100 100 7 400 i 11 5.84 100 100 '7 1000- 15 1811.1 100 100 7 1000 15 i 12.3 100 100 7 1000 24 i 0.2 .100 100- 7. 500-i i. 5.3 .100 100 7 500 5 15 5. 46' 100 100 v 7 600 "42 14 2.38 1 1100100- 7 700 1 452 13- 1:28 100 100 7 600 ,110 22 7.9. 100 100 7 500 "1' iass 100 100 1 600 14 j 3.70 100 100 7 400 g 3 19 1 5.2 "100 100 7 600 I8 -19 5.71 100 100 7 700 .13 v 34 Sn (ous) chloride 8.19 100 100 7 400 258 Unextruded casein 100 7 500 20 40 10 I 1011 Y i=insolubla in thisformula. j-slightly soluble but jells almost immediately. L

The metal.compounds'given in the above list are not substances which, inthe presence .of water, act as solubilizing agents for casein.

' As indicated in Tablel, nearly all the casein compounds listed aresolubledn ammonia, while a few are insoluble even when.an excess of.ammonia employed All the compounds are in- It willbenoted (see lastlineof table) that the glue preparedfrom casein in its natural condition gave viscosity values of '40; at 20 minutes, 10 at 5 hours and wasa firm jell'at 24 hours. Some of the casein compounds "(indicated by theletteriin columnG) did not dissolve in this formula',"while others(indicated'bythe letter 1') 100 parts of this] the same proportion ofwater as before, and the viscosity determined at 3 the same intervalsand dissolved to some extent forming a stifi mass -which 'did notliquefysufiiciently for a viscosity determination to be made, showingthatthey are unsuitable for use in this formula but'not necessarilyunfit foruse other glue formulas. It

153 simple. mechanical mixture ofthe same ingredients. v

cobalt carbonate extruded product E is brick red. 7

In some cases the products are "of different color, e. g. in thecase ofw 'the'M mixture isof a light brown color while the Table 2 5 Amt.oi.'Amt. of Amt. of Amt. 0i A nt..2b?, Viscosity Compound used compoundcasein g 533: water, animouiai oi solution t used used c g ..used usedat 70 F.

Bi hydroxide 7.09 M 500 7 33 Do 500 7 38 Co carbonate" 9.48 M 600 71 400Do 'E I 600 7 20 Zn carbonate 5.18 M '400 '7 D0 E ,400 7. 4 Mn citrate9.74 M 400 7 60 .D 1 E 400 -R Kdicbromat 10.95 M 800 7 I 500 Do E 800 760 Na bisulphat 5.18 M 600 .7 E 180 Do E too 7 .4 .Ca chloride. 1.26 M600 7' 110 D0 E I 600 7 2i ,-lma y be noted that the glue made from thecasein compound of calcium carbonate, which in the early stages hassubstantially the same consistency as that prepared from casein, remainsfluid overnight which is an important advantage-for some purposes, whilethe glue made'from the casein compound of nickel carbonate maintains amore uniformvconsistency over the first few hours and also remains fluidand usable overnight, whereas the casein glue in the same period of timehas passed into an unusable condition.

The compound with cadmium chloride-is insoluble in ammonia and insolublein the glue formula but it is soluble in-sodium carbonate solution.

. It is to be understood that the results recorded in the above tableare not the same as would be obtained by substituting for the extrudedcasein-compound an equal weight of a simple mixture of its components(1. e. casein and the respective salt) which has not been subjected tothe process of kneading and extrusion described above. This is clearlyshown inTable 2 in which the viscosities of ammoniacal solutions ofseveral of the casein-compounds are compared with those obtainedbysimilarly dissolving a proportionate mixture of the unextrudedcomponents. The compositions of the respective casein-compounds are thesame as in Table 1 but they are stated here on a percentage basis forconvenience. The parts are by weight. The amount of salt used isrecorded in the second column and the amount of casein used in the thirdcolumn, these together making 100. One hundred parts of the mixture aredissolved directly in the amount of water shown inthe sixth column with7 parts of 26f B. ammonia added, heated to 160 F. with stirring andcooled to *F. The Stoermer viscosity of the solution at 70 F. is shownin the last column- A like test was made with parts of the correspondingcasein-compound dissolved in the sameway. In this table the letter Mdenotes the unextruded mixture and E thecorresponding,extrudedwmaterial. In every pair of tests a widedifference of'viscosity is observed, and I believe that this indicatesthat a chemical reaction takes place during the passage of the materialthrough the extrusion press, promoted by'the kneading action, elevatedpressure and temperature and perhaps other causes. The properties of thecasein compounds thereby produced are markedly different from those of aThe differences between the viscosities of the, ammoniacal solutions ofthe compounds in Table 2 and those of the corresponding solutionscomtaining the same proportion of dry compourrds and water in Table 1 aredue to the difierent method used in making the solutions. Ithas'beenstated-that in Table 1 I first mixing 1 part of dry'subs'tance' with4parts the solutions weremade by of water, heating and subsequentlydiluting'with water to the required amount,-while -in Table 2 the fullamount of water was .added initially.

' With some of the substances it made a difference whether the water orall in one step.

was added' several step's ''On account of the widely different chemicaland physical properties of the compounds'listed in Table 1 they areadapted fora wide variety off purposes. The compound of aluminumborat'e,'.

for instance, when dissolved in presence ofanimonia, with as much as 10parts of water base thickerconsistency or body-than the correspondingcasein solution with only 5 parts ofwater, and onaccount of thisproperty of forming heavybodied solutions it can be used with advantagein paper-coating, since'the-liquid coating will lie on the surface ofthe paperinstea'di" of 'sinking deeply into the fibre. Combinations ofcasein with saltsof lead, mercury, arsenicycopper and the like areuseful in the making of insecticides. They provide, a very satisfactorymeans or apply ing to vegetation, asa spray, solution of poisonousproducts which adhereto the foliage and-produce the desired effects; orin a finelypulverized form they can be applied as a dust with or withoutthe additionof a, small proportion of alkali so that when the foliageissliglitly moist or becomes damp 60 I with dew the powderedcompoundwill adhere to the foliage sumciently' to be practical for aeusinsecticide.

I believethat some of thecornpounds will .have

particular value as fertilizers or plant-foods. It' I I is known, forexample, that certain 'typespf"vege tatlon require a small amount theavailability of such material in the so'il ispf great importance. In thecasein-manganese com bin'ations the manganese is present in -a n,espe -Jcially available form.v v l of manganese, and

The combinations of casein with made by this process; which are solublein 'airi" monia, when applied to'paper and dried form an insolublecoating without the addition of any other substance.

It may be 'hote'din Table 2.

consistency of the ammoniacalsolution of the extruded product and amixture of casein with potassium dichromate similarly dissolved with 8parts of water, the viscosity of the former being 60 and that of thelatter 500 which represents a thin watery solution of less commercialvalue. With a lesser proportionof .water the casein dichromate compoundhas a heavy, almost jellylike consistency. g

The above-mentioned casein; combinations with lead hydroxide and bismuthhydroxide provide glues in the glue-formula above described which remainfluid over a much longer period than those prepared directly from thecasein.

I believe that some of the casein compounds produced by this process e.g. those of bismuth and iron have therapeutic value.

Theca'sein used in these tests was a commercial grade made byprecipitation with hydrochloric usually employed in the art of plasticsbut I may also use. caseinprecipitated by otheracids.

For making, the tests of viscosity in ammoniacal solution the extrudedand dried product was ground .to pass through a standard 24 mesh wirescreen. The materials used in the glue formula tests were ground to passa 50 mesh wire screen in order to facilitate dissolving in theglue-mixing operation which is conducted at ordinary room temperature.

It mayin some cases be possible to omit the drying and comminuting step,e. g. where the extruded material (say ribbon) is run directly into analkaline solution to dissolve the casein content and/or otheralkali-soluble constituents present. a

Instead of drying the ribbon and then comminuting the dry product, itmay be feasible in some cases, to comminute the ribbon, and to then drythe comminuted material, followed, if desired, by further grinding.

The final product will be ordinarily dissolved in an alkaline solutionbefore use. But in some cases alkali is added before the final extrusionstep, and .the product can then be dissolved in water.

The term not. strongly alkaline as used in the appended claims isintended to include not only salts and compounds which in aqueoussolution or suspension, are neutral or acid to indicators like litmus,but also substances such as lead hydroxide which when suspended in watermay give a very slightly alkaline reaction, to litmus, but are notsufllciently alkaline to act as solvents for casein. I

I claim:

1. As a product, a homogeneous combination of acid-precipitated caseinwith a compound selected from the group consistingof metal salts, metalhydroxides and ammonium salts, said compound being not suificientlyalkaline in reaction to constitute a solubilizing agent for casein, andwhich compound is capable of reacting with moist casein, said productbeing extruded under heavy'pressure while containing less water thancasein. z

2. As a product, a. homogeneous combination of acid-precipitated caseinwith a compound selected from the group consistingof metal salts, metalhydroxides andammonium salts, said compound being not sufficientlyalkaline in reaction to constitute a solubilizing agent. for casein, andwhich compound is capable of reacting with moistin alkaline solution Ithat there is a wide. difference in the physical casein, said productbeing extruded under heavy pressure while containing less water thancasein, such product being insolubleinwat'er but soluble 3. As aproduct, a homogeneous combination of acid-precipitated casein with acompound selected from the group consisting of metal salts, metalhydroxides and ammonium salts, said compound being not sufficientlyalkaline in reaction to constitute a solubilizing agent for casein, to-

ether with an alkaline substance which renders thejproduct soluble inwater, and, which compound is capable of reacting with moist casein,

said product being extruded under heavy pressure while containing lesswater than'casein.

4. As a product, a. homogeneous combination of acid-precipitated caseinwith a compound selected from-the group of heavy metal compoundsconsisting of'metal salts, metal hydroxides and ammonium salts, saidcompound being not sufiicientlyalkaline in reaction to constitute asolubilizing agent for casein, and which compound is capable of reactingwith moist casein,

said product. being extruded under-heavy pres- I sure, while containingless water than casein." 5. As a productga dried homogeneous combinationof acid-precipitated casein with a cornpound selected from the groupconsisting of metal salts, metal hydroxides and ammonium salts, saidcompound being not sufiiciently alkaline in re-' action to constitute asolubilizing agent for casein, andwhich compound is capable of rea minorfraction of the amount of said casinJ 7. As a product, a composition ofacid-precipi-,

tated casein combined with a metal salt, which, in the presence of'water,'does not constitute a casein solvent, such product being solublein ammoniacal solution, such product being extruded under high pressurewith an amount of water which is only a minor fraction of the amount ofsaid casein. I 7

8. As a product, an extruded reaction'product of casein with a heavymetal compound ,'such product being soluble in caustic soda solution,such product being extruded under high pressure with an amount of waterwhich-is only a. minor fraction of the amount of said'casein;

' 9. As a product, an extruded reaction product of casein with a heavymetal compound, such product being soluble in ammoniacal solution,

such product being extruded under high pressure with an amount of waterwhich is only'a minor fraction of the amount of said casein. Y I '1' 10.A process of makinga casein product of thecharacter set forth, whichcomprises adding to moist casein containing less water'than casein,

the conditions stated, well kneading the mixture under superatmosphericpressure and subse quently drying the kneaded mixture in the formcapable of reacting upon casein, well kneading the mixture,'extrudingthe same through a narrow opening and drying the extruded material inthe fonn of pieces which have at least one small dimension.

12. A process of making a casein productof the character set forth,which comprises adding to moist casein containing less water thancasein, a compound of a metal capable of reacting upon casein to form awater-insoluble compound, well kneading the mixture, undersuperatmospheric pressure, and converting the kneaded mixture into theform of pieces which have at least one small dimension.

13. A process of making a casein product of the character set forth,which comprises adding a heavy metal salt to moist acid-precipitatedcasein containing less .water than casein, well kneading the mixtureunder superatmospheric pressure, and drying the kneaded mixture in theform of pieces which have at least one small dimension.

14. A process of making a casein product of the character set forth,which comprises adding a hydroxide of a heavy metal to moist caseincontaining less water than casein, well kneading the mixture undersuperatmospheric pressure and drying the kneaded mixture in the form ofpieces which have at leastone small dimension.

15. A process of making a casein product of T I the character set forth,which comprises adding to moist casein containing less'water thancasein,

a salt selected from the class consisting of nonbasic salts of metalsand non-basic salts of ammonium, which salt is capable of reacting uponcasein, well kneading the mixture under superatmospheric pressure anddrying the'kneaded mixture in the form of pieces which'have at leastonesmall dimension."

16. Process of claim 10, followed by grinding v the dried product.

1'7. A process of making a casein product of the; character set forth,which comprises adding to moist casein containing less water thancasein, achemical compound selected from the herein described classconsisting of non-alkalinesalts of heavy metals, hydroxides ofheavy'metals, salts ofammonium, calcium, strontium and magnesium whichwhen mixed with water give liquids which are not strongly alkaline, andthe salt of these metals with organicacids; salts of anti-' mony,aluminum and cadmium; soluble chromates and dichromates; acid sodiumsalts .of

mineral acids, lithium chloride andmixtures of the above, capable ofreacting upon casein under the conditions stated, well kneading themixture under superatmospheric pressure and subse-j

